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Atmospheric aerosols are often mixtures of inorganic and organic material.Organics can represent a large fraction of the total aerosol mass and arecomprised of water-soluble and insoluble compounds. Increasing attention waspaid in the last decade to the capability of mixed inorganic/organic aerosolparticles to take up water (hygroscopicity). We performed hygroscopicitymeasurements of internally mixed particles containing ammonium sulfate andcarboxylic acids (citric, glutaric, adipic acid) in parallel with anelectrodynamic balance (EDB) and a hygroscopicity tandem differentialmobility analyzer (HTDMA). The organic compounds were chosen to representthree distinct physical states. During hygroscopicity cycles coveringhydration and dehydration measured by the EDB and the HTDMA, pure citric acidremained always liquid, adipic acid remained always solid, while glutaricacid could be either. We show that the hygroscopicity of mixtures of theabove compounds is well described by the Zdanovskii-Stokes-Robinson (ZSR)relationship as long as the two-component particle is completely liquid inthe ammonium sulfate/glutaric acid system; deviations up to 10% in massgrowth factor (corresponding to deviations up to 3.5% in size growth factor)are observed for the ammonium sulfate/citric acid 1:1 mixture at 80% RH. Weobserve even more significant discrepancies compared to what is expected frombulk thermodynamics when a solid component is present. We explain this interms of a complex morphology resulting from the crystallization processleading to veins, pores, and grain boundaries which allow for water sorptionin excess of bulk thermodynamic predictions caused by the inverse Kelvineffect on concave surfaces

A combined particle trap/HTDMA hygroscopicity study of mixed inorganic/organic aerosol particles